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Publication numberUS3265461 A
Publication typeGrant
Publication dateAug 9, 1966
Filing dateFeb 12, 1965
Priority dateNov 2, 1960
Also published asDE1155088B
Publication numberUS 3265461 A, US 3265461A, US-A-3265461, US3265461 A, US3265461A
InventorsLuetzel Gerhard, Rohland Werner, Tartter Arnold, Barts Guenter, Dietrich Werner, Federkiel Wilhelm, Mueller Roland
Original AssigneeBasf Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Dye and hexahydro-1, 3, 5-triacryloyl-s-triazine or derivative thereof composition and dyeing therewith
US 3265461 A
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Description  (OCR text may contain errors)

United States Patent DYE AND HEXAHYDRO 1,3,5 TRIACRYLOYL s- TRIAZINE 0R DERIVATIVE THEREOF COMPO- SITION AND DYEING THEREWITH Gerhard Luetzel and Werner Rohland, Ludwigshafen (Rhine), Arnold Tartter, Lambsheim, Pfalz, Gucnter Barts, Ludwigshafen (Rhine), Werner Dietrich, Manuheim, Wilhelm Federlriel, Frankenthal, Pfalz, and Roland Mueller, Ludwigshafen (Rhine), Germany, assignors to Badische Aniliu- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany N0 Drawing. Filed Feb. 12, 1965, Ser. No. 432,403 Claims priority, applicationgglgrmany, Nov. 2, 1960,

59, 2 Claims. (Cl. 884) This application is a continuation-in-pant of our copending application Serial No. 148,852, filed October 31, 1961, now abandoned.

The invention described and claimed in this application relates to a process for dyeing and/ or printing textile materials in which the material is treated, in the presence of a strongly alkaline-reacting agent, with a dye which has one or more reactive hydrogen atoms, preferably attached [by way of nitrogen, oxygen or sulfur, or which is capable of making available one or more such hydrogen atoms during the dyeing and/ or printing process, and with an uncolored polyfunctional compound which bears three H C=CH-CO groups attached by way of nitrogen or which is capable of forming three such groups during the dyeing and/ or printing process, if necessary at elevated temperature.

The invention further relates to dye preparations for dyeing and/ or printing textile materials which are characterized by a content of an organic dye which has one or more reactive hydrogen atoms, preferably attached by way of nitrogen, oxygen or sulfur, or is capable of forming one or more such hydrogen atoms during the printing :and/or dyeing of the textile material in the presence of strongly alkaline-reacting agents, and also by a content of an uncolored polyfunctional compound which bears three H C=CHCO- groups attached by way of nitrogen or which is capable of forming three such groups during the dyeing and/or printing of the textile material in the presence of strongly alkaline-reacting agents, and optionally by a content of la dispersing agent and/or protective colloid and/or dyeing and/ or printing auxiliaries.

It is known to the expert in the field of dyeing and printing textile materials with organic dyes that the [fastness properties of the very strong dyeings and prints obtained with substantive dyes leave much to be desired. Reactive dyes give dyeings and prints with good fastness properties, but relatively large amounts of the reactive dye are not fixed on the fiber during the dyeing and printing of the textile materials. It has therefore been desirable that a process should be found which would combine the advantages of dyeing and printing textile materials with substantive dyes with the advantages of dyeing and printing textile materials with reactive dyes, without having the disadvantages of these two methods. In other words, the new process should make possible the dyeing and printing of textile materials with high dye yields such as when using substantive dyes, while at the same time achieving fastness properties of the dye- Patented August 9, 1966 ings and prints such as are obtained when using reactive dyes.

We have now found that textile materials, such as fibers, threads, filaments, flock, woven fabrics and knitted fabrics can be dyed and/or printed fast to washing by treating the material in the presence of an agent having a strong alkaline reaction with a dye which contains one or more reactive hydrogen atoms, preferably attached by way of nitrogen, oxygen or sulfur, or is capable of forming one or more such hydrogen atoms during the dyeing and/ or printing process, and with an uncolored polyfunctional compound which bears three groups or is capable of forming three such groups during the dyeing and/or printing process, if necessary at elevated temeperatures.

The new process preferably serves for dyeing and/or printing textile materials of native and/or regenerated cellulose. It is also applicalble to textile materials of polyacrylonitrile or copolymers of acrylonitrile with other vinyl compounds or textile materials of linear polyesters, for example polyethylene glycol terephthalate, polyesters on the basis of terephthalic acid and p-dimethylol-oyclohexane, or textile materials of linear polyamides such as poly caprolactarn.

Strongly alkaline-reacting agents are preferably inorganic agents, especially alkali metal hydroxides or carbonates, such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, but also include compounds which are converted under the usual conditions of dyeing or printing into strongly alkalinereacting agents, for example alkali metal bicarbonates, such as sodium or potassium bicarbonate, and also dialkali or trialkali metal phosphates, such as disodium phosphate or trisodium phosphate. Mixtures of two or more of these strongly alkaline-reacting agents may also be used.

Suitable organic textile dyes include acridine dyes, anthraquinone dyes, azine dyes, azo dyes, such as monoazo, disazo or polyazo dyes, azomethine dyes, benzoquinone dyes, naphthoquino-ne dyes, quinoline dyes, quinophthalones, indigoid dyes, indophenols, indoanilines, indamines, leuco vat dye esters, metal complex dyes, naphthalimide dyes, nigrosines and indulins, nitro dyes, nitroso dyes, :oxazine dyes, dioxazine dies, oxidation dyes, pyrazolone dyes, tetrazaporphin dyes, such as phthaloicyanine dyes, methine dyes, polymethine dyes, sulfur dyes, stilbene dyes, triarylmethane dyes, diarylmethane dyes, thiazine dyes, thiazole dyes, thioxanthone dyes and xanthene dyes, but also so called optical bleaches, as for example fluorescent compounds of the stilb ene, benzimidaziole, benzoxazole and benzothiazole series. It is also possible to start from mixtures of two or more dyes.

The dyes of the above-mentioned kind bear one or more reactive hydrogen atoms, preferably attached by way of nitrogen, oxygen and/or sulfur, for example in the form of primary or secondary amino groups, sulfonic acid amide groups, sulfonic acid alkylamide groups, such as those with low molecular Weight alkyl radicals, sulfonic acid arylamide groups, such as sulfonic acid anilide groups, carboxylic acid amide groups, carboxylic acid alkylamide groups, such as those with low molecular weight alkyl radicals, hydroxyl groups and/or sulfhydryl groups. Those dyes are of special technical interest which contain one or more reactive hydrogen atoms in the form of HO-alkylene groups, H N-alkylen'e groups and/or sulfonic acid alkylamide groups preferably with low molecular weight alkylene groups or alkyl groups, for example dyes with H NSO groups, HO.CH .CH groups, H N.CH .CH groups,

HO.CH .CH .NH.SO

groups and/or H C.NH.SO groups. Dyes which contain one or more reactive hydrogen atoms attached by way of carbon, for example the dye of the formula:

(obtainable by the process of US. Patent No. 2,873,280) are also suitable for the process of this invention. Dyes which are capable of making available one or more reactive hydrogen atoms, preferably attached by way of oxygen, nitrogen or sulfur, during the dyeing and/or printing process, are for example dyes having methylene ether groups or methylene ester groups. These groups are converted into methylol groups during the process.

The expression dyes having one or more reactive hydrogen atoms is intended to convey that the dyes of the specified kind have one or more, generally 1 to 11, active hydrogen atoms which enable these dyes to react after the manner of a so-called Michael reaction. The new process may be applied both to dyes which are free from water-solubi-lizing groups and to water-soluble dyes. The latter dyes as a rule bear one or more sulfonic acid groups and/or carboxyl groups as the watersolubilizing groups. Dyes which contain one or more sulfonic acid alkylamide groups, such as sulfonic acid- (B-hydroxyethyD-amide groups or sulfonic acid methylamide groups as water-solubilizing groups, may be advantageously used for the process according to this invention. The dyes used may be substantive, but it is also, possible to use so-called reactive dyes which are capable of chemically combining with the material to be dyed or printed. In the case of substantive dyes, the new process gives an improvement in the fastness properties of the dyeings and prints, and in the case of reactive dyes the proportion of dye which is fixed washfast on the goods being dyed or printed is increased and consequently the yield of the reactive dyes is considerably improved. -As uncolored polyfunct-ional compounds which have three H @CH-CO groups attached by way of nitrogen, there are used one or more compounds, preferably the hexahydro-l,3,S-triacryloyl-s-triazine (N,N,N-triacryloyl-trimethylene triamine) known from the literature, for example from Berichte de deutschen chemischen Gesells'chaft, vol. 81 (1948), pp. 527 to 531, and from J. Am. Chem. Soc., vol. 70 (1948), pp. 3079 to 3081, which is obtainable in a simple way by the action of acrylonitrile on formaldehyde. Uncolored polyfunctional compounds which are capable of forming three H C=CHCO groups during the dyeing and/or printing process according to the invention, include hexahydro-1,3,5-tri-(flchloropropionyl)-s-triazine (N,N',N"-tris (B chloropropionyl)-trimethylene triamine) known from the above-mentioned literature or the quaternary derivatives of the general formula:

obtainable by the action of tertiary amines, such as pyri-.

dine, quinoline, N-methylirnidazole or N-vinylimidazole, on the said compound.

Fixation of the dye on the goods being dyed, which is usually effected at temperatures between 15 and 200 C., is possible by the new process even at room temperature, i.e., at about 15 to 30 C. It is however preferable to fix the dye in the usual way, for example by steaming or by dry heating, at temperatures between 30 and 200 0, preferably between 40 and C., in so far as the goods to be dyed and/ or printed permit the use of these temperatures. The duration of the fixing process may vary within wide limits because it is dependent on the nature of the dye used, on the uncolored polyfunctional compounds used, on the strongly alkaline-reacting compounds used, on the goods being dyed and on the temperature used for the fixing; it may readily be determined by a preliminary test. It is advantageous to fix the dye on textile material of cellulose by steaming or by dry heating at 70 to 1500 C. In this temperature range, the fixation of the dye is usually completed within about 5 to 10 minutes.

The process according to the invention may be carried out by treating the material to be dyed and/ or printed with. the strongly alkaline-reacting agent, the dye and the uncolored polyfunctionalcompound of the abovementioned kind successively and in any sequence. It is however preferable to treat the materialrto be dyed or printed with a dyebath or printing paste which contains the strongly alkaline-reacting agent, the dye and the uncolored polyfunctional compound of the above-mentioned kind. The material thus treated is rinsed in the usual way, soaped if necessary and finished ofi. It may be of interest to start with dye preparations which, besides the dyes, contain the uncolored polyfunctional compounds of the above-mentioned kind, if desired together with dispersing agents and/or protective colloids and/ or dyeing or printing auxiliaries.

As a rule, these dye preparations consist of a mixture or dispersion of 5 to 6-5 partsby weight of dye and 5 to 65 parts by weight of uncolored polyfunctional compound of the above-mentioned kind together with 0 to 60 parts by weight of dispersing agent, 1 to 35 parts by weight of protective colloid, 0 to 5 parts by weight of dyeing or printing auxiliary and 0 to 50 parts by wei-ght'of water and/or solvent miscible with water. Mixtures of two or more dyes, uncolored polyfunctional compounds, dispersing agents, dyeing and/or printing auxiliaries and/or water-miscible solvents may also be used.

Examples of dispersing agents are lignin sulfonate, the condensation product of sulfonated phenol with urea andformaldehyde' and the condensation product of naphthalene-Z-sulfonic acid and formaldehyde. Examples of protective colloids are partly acetylated polyvinyl alcohol of the K-valve 30 (K-valve measured in water according to Fikentscher; for method see H. Fikentsoher, cellosechemie, vol. 13, 58 (1932)), carbioxymethylcellulose, the sodium salt of the copolymer of maleic acid and styrene in the mole ratio 1:1, polyvinylpyrrolidone of the K-value 30 and dextrin. Examples of dyeing and/or printing auxiliaries are antioxidants, such as hydroquinone, or wetting agents, such as the sodium salt of s-ulfon-ated oleic acid-N-methylcyclohexylamide, the sodium salt of sulfonated oleic acid cyclohexylamide andbenzylnaphthalene sulfonic acid.

Mixtures, if necessary dispersed, of 5 to 65 parts by weight of at least one dye which has 1 to 11 reactive hydrogen atoms attached by way of nitrogen, oxygen, sulfur or canbon is capable of forming 1 to 11 such hydrogen atoms during dyeing and/or printing textile material in the presence of strongly alkaline-reacting agents, 5 to 65 parts by weight of at least one uncolored poly'functional compound of the above-mentionedkind, 0 to 60 parts by weight of at least one dispersing agent, 1 to 35 parts by weight of at least one protective colloid, to parts by weight of at least one dyeing and/ or printing auxiliary and 0 to 50 parts by weight of water, at least one water-miscible solvent or a mixture of water with at least one water-miscible'solvent are of special technical interest as dye preparations.

For these mixtures, dispersed if necessary, the preferred dyes are acridine dyes, anthraquinone dyes, azo dyes, for example monoazo, disazo or polyazo dyes, such as tetrakisazo dyes, azomethine dyes quinoline dies, indamines, metal complex dyes, for example of cobalt, chromium, copper and iron, nigrosines, nitroso dies, dioxazine dyes, pyrazolone dyes, phthalocyan-ine dyes, for example copper, nickel or cobalt phthalocyanines, methine dyes, triarylmethane dyes, xanthene dyes or optical bleaches of the stilbene series.

The uncolored polyfunctional compounds are conveniently used together with dispersing agents and/or protective colloids in finely divided form or as solutions in water-miscible solvents. Suitable water-miscible solvents for this purpose are especially dia-lkylcarboxylic acid amides, such as dimethylformamide or dimethylacetamide, lactams, such as N-methyl-2pyrrolidone, ethers, such as glycol ether or tetrahydrofu-rane, but also alcohols, such as methanol, ethanol or isopropanol, ketones, such as acetone, and/ or organic acids, such as formic acid or acetic acid.

The dyebaths and printing pastes according to this invention may contain, besides the strongly alkaline-reacting agents, dyes and uncolored poly-functional compounds, the usual dyeing auxiliaries or printing auxiliaries, in so far as these auxiliaries do not react in an undesirable way with the initial materials necessary for the process. Such dyeing auxiliaries and/ or printing auxiliaries include surface-active compounds, such as alkysulfionates; compounds which prevent migration of the dyes, such as sodium acetate; agents which improve the solubility and fixation of the dyes, such as urea; and thickening agents, for example oil-in-water emulsions, tragacanth thickenings, alginates or methyl-cellulose.

As a rule, the dyebaths and printing pastes are applied to the goods to be treated by impregnation by means of a pad or by printing. It is possible 'however, to carry out the new process with the aid of other conventional dyeing machines and apparatus, such as jiggers, vats, winch becks or high-temperature dyeing apparatus. In the case of cellulose textile materials it is possible to carry out a so-called resin finishing, for example a creaseproof finishing, simultaneously with the new dyeing and/ or printing process.

In the new process of dyeing and/or printing textile materials, for each 100 parts of one or more dyes having one or more reactive hydrogen atoms, preferably attached by way of nitrogen, oxygen or sulfur, there are used in general about to 200 parts of a strongly alkaline-reacting agent and about to 400 parts of an uncolored polyfunctional compound of the above rnentioned kind.

The dyeings and prints obtainable according to this invention are characterized in general by excellent wet fastness properties. When starting from water-soluble dyes it is recommendable to use dyes which have only a slight aflinity for the goods to be dyed in order to facilitate washing out of any parts of the dye which have not been fixed. In the case of water-insoluble dyes, dyeings and prints of remarkably good rubbing and solvent fastness are obtained according to the new process.

The new process for dyeing and/or printing textile material difiers from the process known from German patent specification No. 909,068 by considerably improved fastness to washing and especially to soda boiling of the dyeings and prints obtaintable therewith on cellulosic textile material.

An essential advantage of the process according to the invention over the known dyeing and printing methods with so-called reactive dyes resides in the fact that dyes without reactive groups may be used for the new process andthe-se, contrasted with the known reactive dyes can be stored practically indefinitely.

The invention is illustrated by, but not limited to, the following examples. The parts and percentages specified in the examples are weight units unless otherwise stated. Parts by weight bear the same relation to parts by volume as the kilogram to the liter measured under normal conditions.

EXAMPLE 1 A solution of 20 parts of the dye of the formula:

OHz.CHz. O H

CH2.CH2. O H

(obtainable by coupling diazotized 4-aminophenyl-[2-hydroxy-3-(N,N-bis-2-hydroxyethyl) aminopropyl] ether with 1 hydroxy-8-acetylaminonaphthalene-3,S-disulfonic acid) and 20 parts of sodium carbonate in 1000 parts by volume of water is mixed with parts by volume of a 10% solution of hexahydro-l,3,S-triacryloyl-s-triazine in dimethylformamide. Cotton fabric is padded with this mixture, dried and thereafter steamed for about 5 to 8 minutes at C. The material is then rinsed and soaped as usual, only a small amount of dye being washed out. A bluish-red dyeing is obtained with very good wet fastness'properties.

By using 240 parts by volume of a 10% solution of hexahydro-l,3,5-triacryloy1- s triazine in dimethylformamide instead of 80 parts by volume, still deeper dyeings are obtained,

EXAMPLE 2 A mixture of 20 parts of the sodium salt of the dye of the Formula 1V used in Example 1 and 30 parts of sodium bicarbonate is stirred into a mixture of 470 parts by volume of water, 80 parts by volume of a 10% solution of hexahydro-l,3,S-triacryloyl-s-triazine in dimethylformamide and 400 parts of sodium alginate thickening (containing 40 parts of dry substance in 1000 parts). Cotton fabric is printed with the printing paste thus obtained, dried and then steamed for about 5 to 8 minutes at 100 C. The printed material is then rinsed and soaped as usual. Bluish-red prints of very good wet fastness properties are obtained.

EXAMPLE 3 20 parts of a copper phthalocyanine dye which contains about two to three HO S groups and about one to two H N.CH .CH .NH.SO groups and which is obtainable by reaction of copper phthalocyanine tetrasulfonic acid chloride with monoacetylethylene diamine and subsequent splitting off of the acetyl radical, is dissolved in 1000 parts by volume of an aqueous mixture which contains 20 parts of sodium carbonate, 250 parts by volume of a 10% solution of hexahydro-l,3,S-triacryloyl-s-triazine and 200 parts of urea. Cotton is impregnated with this solution, dried and then thermofixed for 5 minutes at C. (i.e. heated dry at 150 C.). After the usual aftertreatment, a deep turquoise blue dyeing with very good wet fastness properties is obtained.

EXAMPLE 4 A solution of 20 parts of the dye specified in Example 3 in 1000 parts by volume of water is mixed with 10 parts by volume of aqueous caustic soda solution of 38 B. and 80 parts by volume of a 10% solution of hexahydro-l,3,S-triacryloyl-s-triazine in dimethylformamide. This mixture is applied to rayon staple fabric by means of a pad. Then the fabric is dried and thereafter steamed at 100 C. After the usual finishing of the material by rinsing and s oaping, by which only a very small amount of dye is lost by washing out, a turquoise blue dyeing of outstanding wet fastness properties is obtained.

EXAMPLE A cotton fabric which has been dyed 2% in the usual way with the direct dye Cotonerol V extra (Colour Index, 2nd edition 1956, vol. 3, p. 3306, C.I. No. 35,430) on a winch beck or on a jigger, is padded with a solution which contains in 1000 parts by volume 20 parts of sodium carbonate and 80 parts by volume of a solution of hexahydro-1,3,S-triacryloyl-s-triazine. The material is then dried and steamed for about 5 to 8 minutes at 100 C. The deep grey dyeing thus obtained is superior in its wet fastness properties to a dyeing carried out for comparison in the way conventional for direct dyes.

EXAMPLE 6 V A solution of 20 parts of the copper phthalocyanine dye obtainable as described in the third paragraph of this example in 1000 parts by volume of water is mixed with 10 parts by volume of aqueous caustic soda solution of 38 B. and 80 parts by volume of a 10% solution of hexahydro-l,3,S-triacryloyl-s-triazine in dimethylformamide. Cotton fabric is padded with this mixture, steamed for 5 minutes at 100 C., rinsed and then soaped. A turquoise blue dyeing of great depth of color and with outstanding wet fastness properties is obtained.

A turquoise blue dyeing prepared for purposes of comparison with the same dye in the manner usual for reactive dyes is considerably weaker in color than the dyeing obtained according to the preceding paragraph.

The copper phthalocyanine dye used above can be prepared as follows: a solution of 30 parts of the hydrochloride of 1-amino-4-chlorobutine-(2) in 150 parts of water is stirred into an aqueous paste of 250 parts of ice, 250 parts of water and 50 parts of copper phthalocyanine- 4,4',4",4'"-tetrasulfonic acid chloride, and a pH of about 7 is set up in the mixture by adding 10% aqueous sodium carbonate solution. The mixture is stirred for several hours at room temperature and, when the pH no longer changes even when no sodium carbonate solution is added, such an amount of dilute hydrochloric acid is added that a pH of 2 to 3 is achieved. The deposited dye is filtered oil and dried under reduced pressure at a low temperature.

Instead of the above-identified dye, there may also be used for the dyeing process explained in the first aragraph of this example Diazo Navy Blue R (Colour Index, 2nd edition 1956, vol. 3, p. 3301, Q1. No. 35,080), Sirius Light Red Violet RL (Colour Index, 2nd edition 1956, vol. 3, p. 3203, C.I. No. 25,410) and the dye obtainable by reaction of copper phthalocyanine trisulfonic acid chloride with ammonia, which bears one HO S group and two H N.SO groups.

Further dyes which may be used in the dyeing process described in the first paragraph of this example may be obtained by coupling diazotized 1-aminobenzene-2-sulfon-ic acid-(,B-aminoethyl) amide, diazotized 1-aminobenzene-4-sulfonic acid amide, diazotized 1-aminobenZene-4- sulfonic acid-(fl-hydroxyethyl) amide or diazotized 1- .aminobenzene-4-sulfonic acid-bis-(,B-hydroxyethyl) amide with the following compounds capableof coupling:

These monoazo dyes yield dyeings in the shades indicated in the table opposite the coupling components.

8 EXAMPLE 7 20 parts of a dye preparation which contains 10 parts of the dye of the formula:

(V) obtainable according to the process of German patent specification No. 742,939 is stirred into 1000 parts of 1W3.- ter and mixed with 12 parts of hexahydro-1,3,5-(fl-chloropropionyl)-3-triazine and 3 parts of polyvinyl alcohol while heating to 40 to 50 C. 20 parts of potassium carbonate is introduced into the solution cooled to room temperature. Cotton fabric is impregnated with this dyebath on a pad. The dyed material is then dried, steamed for 5 to 8 minutes at C. and finished oil as usual. A yellow dyeing of very good wet fastness is obtained.

By using 20 parts of the corresponding chromium complexdye instead of the cobalt complex dye above specified, orange dyeings are obtained, similarly with very good wet fastness properties.

EXAMPLE 8 EXAMPLE 9 If 20 parts of one of the dyes specified in Tables I and II be used instead of the dyes of dye preparations specified in foregoing Examples 1, 2, 3, 4, 6, 7, 8 and 9, the procedure being otherwise as described in the said examples, wet-fast dyeings in the shades specified in Tables I and II are obtained on fabrics of cotton or rayon staple.

TABLE I Colour Index, 2d edition 1956, a Serial vol. 3

No. Name of dye Shade Page Serial No. N o.

Alizariuuranol BB 3, 500 62, 510 Grey. Silk inst grey BB 3, 076 15, 715 Do. Celliton last blue green B 3, 505 62, 500 Blue-grey. Celliton fast red GG 3, 017 11,210 Red. Supramin orange R 3,100 17, 770 Orange. Palatin fast yellow 3 GN 3, 051 14, 006 Yellow. Palatin fast Bordeaux BN 3, D85 16, 265 Claret. Palatin fast yellow 5 GN 3, 19,065 Yellow Anthralan Bordeaux B 3, 093 17, 065 Claret Supramin Bordeaux B 3, 093 17, 060 Red-violet Supramin blue R. 3, 092 17, 055 Blue. Fast acid violet 13.. 3, 385 45,186 Violet Wool fast blue FBL 3, 379 44, 510 Blue. Flavonh osnh ine 3, 397 46, 050 Orange. 0.1. Basic Orange 21 3, 402 48, 035 Do. O.I. Fluorescent 3, 341 40, 630 Fluoresces blue. 0.1. Flavaniline 3, 400 47, 025 ellow. C.I. Solvent Black 5. I 0.1. Phenyleue Blue 01. Direct Blue 107 TABLE II Seria Dye Shade of color 1 mmoQ-o ONH@ N =N? C CH Yellow.

HO HOC\ /N 3 OaH (obtainable according to the process described in U.S. patent specification 3,117,962.)

2 Violet.

N: S0zNHz O O R 0 O HzN. 02S N=N (obtainable according to the process described in German Patent Specification 742,939.)

3 Brown.

\ N=N SOZNHl O O-("J I]? HzN.OzS N=NC-C-CHa (obtainable according to the process described in German Patent Specification 742,939.)

4 mmoQ-c ONH--N=N Red.

(Obtainable according to the process described in US. patent specification 8,117,962.)

N O l 5 OFe Green.

E HNOaS (Obtainable according to the process described in British patent specification 805,548.)

6 Violet.

l EN NH,

H038 SO3H (Obtainable according to the process described in British patent specification 908,301.)

TABLE IIO0 ntinued Serial Dye I Shade of color 'l 7 Copper phthalocyamne S0z.NH-N S02 Turquoise blue.

(Obtainab1)e from 1amino-l-aza-4-thiacyclohexane-4,4-di0xide according to the process of U.S. patent specification 0 NH: I 8 S 0 11 Blue.

\J 0 CH;

11 l O NH I Ha C O (obtainable by reaction of 1-a1'11in0-4-br0manthraquinone-Z-sulfonic acid with 1-amino-2,5-dimethoxyanilinei) 9 HzN 0 S Blue-grey.

O 0 Cr (obtainable by coupling diazoti zed l-hydroxy-2-amino-5-nitroben zene with 2-hydroxy-naphthalene-G-sulfonic acid amide and conversion of the mon'oazo dye into the 1:1-chromium complex.)

Hz H: II II C-C 10 [Copper phtha1ocyan1nc](SO -NHCH1CH -N $01M Turquoise blue,

H H2 H9 (Obtaiuable from 1-(B-aminoethyl)-1-aza-4thiacyclohexane-4,4-dioxide according to the process of U.S. patent specification 2,459,771.)

0 ll /CCH3 11. [Nickel phthalocyaninfl s Oz1 ]T-N\ Blue-green.

H O N=C-CH:

(obtainable according to the process described in U.S. patent specification 2,873,280.)

12 [Copper phtha1ocyanine](S O:NH CHrCH2-OH)4 Blue.

(obtainable according to the process described in U.S. patent specification 2,300,572.)

/CH3 13. [Copper phthalocyanineJ-(S Oz-N Blue.

CHr- CHrO )4 V (Obtain-able according to the process described in U.S. patent specification 2,300,572.)

14 [Copper phtha1ocyauine](S O zNCH2CHzOH) Blue.

CHn-CHrOH (Obtainable according to the process described in U.S. patent specification 2,300,572).

(|)H 15 Eopper phthalocyanirieil SOr-NH-Q -0 Green.

+ s H S 0311 CN= N=C N=C N\ CCi O- 0 11038 I] I (obtainable according to the process described in British patent specification 916,532.)

TABLE IIG0ntimLed Serial Dye I i I v I Q I S hede of color 16....... 503E Blue.

2 HOHaO-N N-OHzOH (obtainable according to the process described in U.S. patent specification 3,117,961).

CH H 033 (1) N: O ll 18 N\ /C\ Yellow.

([31 w (J (|3 N=N N N-OH2OH CH-GH (Obtainable according to the process described in U.S. patent specification 3,117,961.)

' 0 19 Q0 C-EN (DH u Red.

(obtainable according to the process described in U.S. patent specification 3,117,961.)

20 N: N NCHzOH Red. (LBJ...

(obtainable according to the process described in U.S. patent specification 3,117,961.)

TABLE II-Oontimtcd Serial Dye Shade of color 0 NH: V ll 21 S 0311 Blue.

1 O P; I IHQN NCH2OH (EH-(L H HOHzC-I I I TCH2OH (obtainable according to the process described in U.S. patent specification 3,117,961.)

III(OH2 'OCH3)2 K OH lTTH-C\ /N @nn. f N(OHzO-C a)z H 03S -S 03H 23 [Cobalt phthalocyanine] Blue.

(obtainable according to the process described in U.S. patent specification 2,300,572.)

24 [3,3-diaz,a copper phthalocyanine](SO NH-CH4-OH) R ddi h-bl (obtainable according to the process described in Us. patent specification 2,300,572.)

25 [Diphenyl copper phthalocyanine](S O 2NH2) 2- Blue-green.

(obtainable according to the process described in U.S. patent specification 2,300,572.)

26 [Monophenyl copper phtha1ocyanine](S 02-NHC2H40H) 3- Green-blue.

(obtainable according to the process described in U.S. patent specification 2,300,572.)

27 [Tetraphenyl copper DhthQIOCYflIlllltfl-(SOzNH2)'1 Green.

3 s (Obtaineble according to the process described in U.S. patent specification 2,300,572.)

(S OzNHC-Hz-CHCH3)2 28 [Tetraphenyl copper phthalocyanine] ()H Green,

(obtainable according to the process described in US. patent specification 2,300,572.)

' (SOzNHCHrOH-CH2OH)2 29. [Copper phthalocyanine] 11 Blue.

(Obtainable according to the process described in US. patent specification 2,300,572.)

(SO NHCH -CH;OH)

30 [Copper phthalocyanine] Blue.

(obtainable according to the process described in U.S. patent specification 2,300,572.)

(s OzNH--S 03H) 1 31. [Copper phtha1ocyanine] Turquoise blue.

SOaH

(Obtainable according to the process described in British patent specification 827,568.)

TABLE II-Oontt'nued Serial Dye Shade of color (S O1NH NHm 32- [Nickel phthalocyanine] Turquoise blue.

SO H

(obtainable according to the process described in British patent specification 827,568.)

OH OH I C-N 33 N N 0% l 1:2-chromium complex Reddish-orenge. 34 \C N SOaH 1:2-cobalt-complex Yellow-brown.

s 0,-NH1

OH OH 35 N =N-O 1: Z-chromium complex. Scarlet.

S 03H l C=N S 02-NH;

C 0 OH OH O C Ha I CN- S 03H N=NC I lzl-chromium complex". Red. N

OH H 038 OH I ON l 37- N=N-O I l g 1:2-chromium complex Red.

- zNHa 1:2-cobelt complex Claret.

1: 2-chromium complex Violet.

' HNC 0 05m 40. 1:2-chromium complex... Blue-violet.

I v v 41 N=(|J 'IEZ-chmrnim'n complex Yellow H l S OzNHg Cl I.

on OH I 42 Q lzl-copper complem n s Redwiolet.

l H2N-S0z H038 NH-OOH3 (obtainable according to the process described in German patent specification 335,809.)

OH O 1 2 h 1 Bl k -c rommm comp ex-' ac 4a v 44 N=N-C 1:2-cobalt complex. Claret.

(Obtainable according to the process described in British patent specification 824,300.)

TABLE II-C'ontimted Serial Dye Shade of color SO H 45. OzNN=N Na Black.

O HN

Or O O H N-01S (Obtainable according to the process described in British patent specification 771,320.)

40 HSN=N Red.

l SOaH (obtainable by coupling diazotized l-amino-4-mercaptobenzene with 1-hydrcxynaphthaleue-i-sulfonic acid.) The dye is kept in the sulfhydryl form by adding 1 gram/liter of sodium dithionite to the dyebath. 7,

EXAMPLE 1O Dye preparation (a) Dispersion of:

8 parts of the dye of Formula V (Example 7), 12 parts of the condensation product of naphthalene-2- sulfonicpacid and formaldehyde, 60 parts of hexahydro-1,3,S-triacryloyl-s-triazine,

2 parts of lignin sulfonate, 16 parts of a partly acetylated polyvinyl alcohol of the K-value 30, and 2 parts of the sodium salt of sulfonated oleic acid N-methylcyclohexylamide.

100* parts The shade is yellow.

Dye preparation (b) Dispersion of:

parts of the dye of Formula VI (Example 8), 15 parts of hexahydro-l,3,5-triacryloy1-s-triazine,

3 parts of the sodium salt of sulfonated oleic acid cyclohexylamide, 3 parts of a partly acetylated polyvinyl alcohol of the K-value 30, and 54 parts of the condensation product of naphthalene-2- sulfonic acid and formaldehyde.

100 parts The shade is red.

Dye preparation (c) Dispersion of:

parts of dye 2 in Table II, 25 parts. of hexahydro-1,3,5-( 3-chloropropionyl)-3-triazine,

5 parts of carboxymethylcellulose, and a 30 parts of the condensation product of naphthalene-2- sulfonic acid and formaldehyde. 7

parts The shade is violet.

. Dye preparation (d) Dispersion of:

30 parts of dye 10 of Table 11, 30 parts of hexahydro-1,3,S-triacryloyl-s-triazine,

6 parts of thesodium salt of a copolymer derived from maleic acid and styrene in the mole ratio 1:1, and

34 parts of lignin sulfonate (purified sulfite cellulose waste liquor).

100 parts The shade is turquoise blue.

Dye preparation (e) Mixture of:

60 parts-of dye 18 of Table 11, 30 parts of hexahydro-l,3,5-triacryloyl-s-triazine, and 10 parts of a partly acetylated polyvinyl alcohol of the K-value 30.

100 parts The shade is yellow.

Dye preparation (1) Dispersion of: Y

15 parts of dye 9 of Table II, 15 parts of the condensation product of naphthalene-2- sul-fonic acid and formaldehyde, 5 parts of polyvinylpyrrolidone of the K-value 30, 15 parts of hexahydro-1,3,S-triacryloyl-s-triazine, and 50 parts of water.

100 parts The shade is blue-grey. p Instead of 50 parts of water, 50 parts of dimethylformamide or a mixture of 30 parts of water'and 20 parts of N-methylpyrrolidone may be used for the dispersion.

present example may be used for the dye preparations- EXAMPLE 11 A mixture of parts of the dye of the formula:

(VII) 8 parts of hexahydro-1,3,S-triacryloyl-s-triazine and 2 parts of a partly acetylated polyvinyl alcohol of the K- value 30 is dissolved in 1000 parts of water and mixed with parts of triethanolamine. The solution thus obtained is applied to rayon staple fabric by means of a pad. The dyed material is then steamed for eight minutes at 100 C. and finished off as usual. A red-violet dyeing with very good wet fastness properties is obtained.

20 parts of pyridine, 20 parts of N-vinylimidazole, 20 parts of N-methylimidazole or 10 parts of an about 50% solution of trimethyl benzylammonium hydroxide in methanol may also be used instead of 20 parts of triethanolamine.

EXAMPLE 12 20 parts of a commercial about 50% preparation of dye 9 of Table II and 100 parts of urea are dissolved together with a dispersion of 12 parts of hexahydro-1,3,5-triacryloyl-s-triazine, 4 parts of the condensation product derived from naphthalene-Z-sulfonic acid and formaldehyde, 3 parts of polyvinyl alcohol of the K-value and 1 part of the sodium salt of sulfonated oleic acid-N-methylcyclohexylamide in 460 parts of water by heating to 70 to 80 C. for about one to two minutes. 400 parts of sodium alginate thickening (containing 40 parts of dry substance in 1000 parts) is then stirred into the cooled solution.

A polyacrylonitrile fabric is printed with the paste thus obtained. The printed fabric is then impregnated by means of a pad with a solution of about 20 to 50 parts of sodium carbonate in 1000 parts of water, dried and steamed for about five minutes at 100 C. Grey prints of outstanding wet fastness properties are obtained. The fabric thus printed may be additionally printed with other dyes and/or treated with agents for improving the fiber properties.

A fabric of copolymer of 95% of acrylonitrile and 6% of methyl methacrylate may be printed instead of a polyacrylonitrile fabric and 30 parts of the following dispersion:

40 parts of hexahydro-1,3,S-triacryloyl-s-triazine, 5 pants of the condensation product derived from naphthalene-Z-sulfonic acid and formaldehyde, 5 parts of polyvinylpyrrolidone of the K-value 30, and 50 parts of water.

100 parts may be used instead of the dispersion of 12 parts of hexahydro-1,3,5-triacryloyl-s-triazine, 4 parts of the condensation product derived from naphthalene-Z-sulfonic acid and formaldehyde, 3 parts of polyvinyl alcohol of the K-value 30 and 1 part of the sodium salt of sulfonated oleic acid-N-methylcyclohexylamide.

22 EXAMPLE 13 15 parts of a dispersion of:

60 parts of hexahydro-1,3,S-triacryloyl-s-triazine, 20 parts of the condensation product derived from naphthalene-Z-sulfonic acid and formaldehyde, 15 parts of a partly acetylated polyvinyl alcohol of the K-value 30, and 5 parts of the sodium salt of sulfonated oleic acid cyclohexylamide 100 parts is dissolved together with 20 parts of the dye of the Formula IV (Example 1) and 20 parts of sodium carbonate in 1000 parts of water. Cotton textile material is introduced into this dyebath and the bath heated to 100 C. while about 50 to 100 parts of sodium sulfate is gradually stirred in. The dyebath is then kept at 100 C. for about 10 minutes to 2 hours. The dyed material is then rinsed and finished oif as usual. A red dyeing with good fastness properties is obtained.

By using 20 parts of a commercial preparation of the dye 2 of Table II instead of 20 parts of the above-mentioned dye, and proceeding otherwise as above described, a violet dyeing of very good fastness properties is obtained.

Instead of cotton textile material, mixed fabrics of rayon staple and a copolymer of of acrylonitrile and 5% of vinylpyridine or textile material of wool, or polycaprolactam, polylauric lactam, polyamino-undecanoic acid or based on adipic acid and hexamethylene diamine may be dyed in the manner described above.

We claim:

1. A process for dyeing and printing textile material of cellulose which consists essentially of contacting said material at temperatures between 15 and 200 C. with the following components:

(a) an uncolored trifunctional compound selected from the group consisting of hexahydro-1,3,5-triacryloyl-s triazine and a hexahydro-s-triazine compound containing attached to the three nitrogen atoms groups which are capable of forming CH =CH-CO groups during the process by action of the strongly alkalinereacting agents,

(b) a strongly alkaline-reacting inorganic agent, and

(c) a water-soluble organic dye having 1 to 11 labile hydrogen atoms in radicals selected from the group consisting of primary amino groups, secondary amino groups, carbamoyl groups, monosubstituted carbamoyl groups, sulfamoyl groups, monosubstituted sulfamoyl groups, hydrazine groups, hydroxyl groups, sulfhydryl groups and labile hydrogens attached directly to carbon, whereby said components a, b, and c are in contact with each other on said material.

2. A dye preparation for dyeing and printing textile materials of cellulose consisting essentially of a mixture of:

(a) an uncolored trifunctional compound selected from the group consisting of hexahydro-1,3,5-triacryloyls-triazine and a hexahydro-s-triazine compound containing attached to the three nitrogen atoms groups which are capable of forming CH =CHCO groups by action of the strongly alkaline-reacting agents,

(b) a strongly. alkaline-reacting inorganic agent, and

(c) a water-soluble organic dye having 1 to 11 labile hydrogen atoms in radicals selected from the group consisting of primary amino groups, secondary amino groups, carbamoyl groups, monosubstituted carbamoyl groups, sulfamoyl groups, monosubstituted sulfamoyl groups, hydrazine groups, hydroxyl groups, sulfhydryl groups and labile hydrogens attached directly to carbon.

No references cited.

NORMAN G. TORCHIN, Primary Examiner.

D. LEVY, Assistant Examiner.

Non-Patent Citations
Reference
1 *None
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3446569 *May 5, 1964May 27, 1969Hoechst AgAqueous solutions of phthalocyanine pigments and process for preparing them
US3617185 *Aug 19, 1968Nov 2, 1971Gaf CorpStable highly concentrated solutions of basic dyes
US3632294 *Nov 12, 1968Jan 4, 1972Ciba LtdQuaternary nitrogen compound assisted reactive dyeing
US3743477 *Jun 24, 1968Jul 3, 1973Sandoz LtdProcess for reserving textiles of natural polyamide fibres and of synthetic fibres dyeable with acid dyes
US3753647 *Mar 5, 1970Aug 21, 1973North American RockwellLiquid oxygen compatible dye penetrant method for metal defect inspection
US3837802 *Jan 4, 1972Sep 24, 1974Ciba Geigy AgProcess for dyeing
US3849162 *May 30, 1972Nov 19, 1974Ciba Geigy AgProcess for preventing the staining of polyamide fibre material treated with fluorescent whiteners
US3860392 *Jan 20, 1971Jan 14, 1975Pechiney Saint GobainColorant compositions and method
US3873265 *Feb 2, 1973Mar 25, 1975Hoechst AgVat or reactive dyes or mixtures thereof and acrylamide or methylene bis acrylamide in alkaline crosslinking and dyeing
US3898036 *Dec 3, 1973Aug 5, 1975Komatsu Seiren CoProcess of dyeing synthetic polyamide fibers
US3929406 *May 21, 1973Dec 30, 1975Deering Milliken Res CorpMethod of detecting defects and composition therefor
US3958933 *May 13, 1974May 25, 1976Ciba-Geigy CorporationDisperse dye, acylating agent, chlorinated hydrocarbon solvent
US3964862 *Sep 21, 1973Jun 22, 1976Ciba-Geigy AgDisperse dye
US3973058 *Dec 23, 1974Aug 3, 1976Monsanto CompanyMethod for printing interlayers for laminated safety glass
US3976425 *Dec 13, 1973Aug 24, 1976American Cyanamid CompanyMonosulfonic acid dye; fixing with steam
US3980426 *Jan 30, 1975Sep 14, 1976Hoechst AktiengesellschaftPolyester mixed fabricsalkali metal formate
US3983588 *Feb 20, 1974Oct 5, 1976Ciba-Geigy AgProcess for the dyeing or printing and simultaneous finishing of cellulose materials
US3989452 *Feb 21, 1975Nov 2, 1976Ciba-Geigy CorporationStable, concentrated solutions of complex metal compounds of azo dyestuffs
US3990839 *Aug 14, 1974Nov 9, 1976Hoechst AktiengesellschaftProcess for obtaining irregular shadow dyeings on polyester fibers and mixtures thereof
US4093415 *Jul 8, 1975Jun 6, 1978Ciba Geigy AgDyeing, optical brighteners, carriers
US4150947 *Jun 11, 1976Apr 24, 1979Ciba-Geigy AgStable, concentrated dispersions of basic dyestuffs
USB497473 *Aug 14, 1974Feb 3, 1976 Title not available
Classifications
U.S. Classification8/541, 8/648, 8/557, 8/924, 8/922, 8/657, 8/553, 8/908, 8/609, 8/606, 8/564, 8/568, 8/573, 8/539, 8/661, 8/912, 8/927, 8/552, 8/663, 8/550, 8/586, 8/563
International ClassificationD06L3/12, C09B62/443
Cooperative ClassificationY10S8/927, Y10S8/908, D06L3/1271, Y10S8/912, Y10S8/924, Y10S8/922, C09B62/443
European ClassificationD06L3/12R, C09B62/443